Composition (e.g. ink or varnish) which can undergo cationic and/or radical polymerization and/or crosslinking by irradiation, based on an organic matrix, a silicone diluent and a photoinitiator

Abstract

The invention aims at improving such compositions by proposing a non -toxic diluent harmless to reactivity and by making these compositions translucent, free from metallic impurities and capable of constituting light-polymerisable varnish with good properties of ductility for leveling and surface coating. This aim is achieved by the invention which proposes a composition comprising an organic polymerisable matrix A, containing cyclo-aliphatic epoxide resins or not, acrylates, alkenyl-ethers or polyols, a silicon diluent B with viscosity less than 100 MPa's, a radical and/or cationic (onium salt) photoinitiator C, optionally a light-sensitising material D, a pigment E and another additive F; provided that when A is a cyclo-aliphatic epoxide resin, B has a metal concentration not more than 100 ppm. The invention also concerns the use of the silicon diluent B for preparing a composition crosslinkable by cationic and/or radical process, under UV radiation, in the presence of a photoinitiator (ink or varnish).

1 . Composition which can undergo cationic and/or radical polymerization and/or crosslinking by irradiation, preferably actinic irradiation and/or with (a) beam(s) of electrons, characterized in that it comprises: 
 A. at least one polymerizable organic matrix and/or at least one partially polymerized organic matrix, comprising (co)monomers and/or (co)oligomers and/or (co)polymers chosen from those containing epoxy (α 1 ) and/or acrylate (α 2 ) and/or alkenyl ether (α 3 ) and/or hydroxyl (α 4 ) reactive functions (frA), with the exclusion of cycloaliphatic epoxides (α 11 );    B. at least one silicone diluent with a reduced viscosity ηr at 25° C. of less than or equal to 200 mPa.s, preferably less than or equal to 150 mPa.s, and even more preferably less than or equal to 100 mPa.s, and comprising: 
 at least one unit of formula (I):  
                     
 in which: 
 a=0, 1 or 2,  
 R 0  is identical to or different from the radicals similar thereto with the same exponent and represents an alkyl, cycloalkyl, aryl, vinyl, hydrogeno or alkoxy radical, preferably a C 1 -C 6  lower alkyl,  
 Z is an organic substituent comprising at least one epoxy and/or acrylate and/or alkenyl ether and/or hydroxyl reactive function (frB), with the condition that at least a portion of the functions (frB) is of the same nature as at least a portion of the functions (frA) of the matrix A,  
 
 and at least two silicon atoms,  
   C. an effective amount of at least one cationic and/or radical photoinitiator,    D. optionally, at least one photosensitizer,    E. optionally, at least one pigment,    F. optionally, at least one other additive.    
     
     
         2 . Composition according to  claim 1 , characterized: 
 in that cycloaliphatic epoxides are not excluded from the list of possible constituents for the matrix (A),    and in that the diluent (B) has a metal concentration of less than or equal to 100 ppm, preferably less than or equal to 50 ppm and even more preferably less than or equal to 20 ppm.    
     
     
         3 . Composition according to  claim 1  or  2 , characterized in that the diluent (B) has a coloration of less than or equal to 200 Hazen, preferably less than or equal to 150 Hazen and even more preferably less than or equal to 100 Hazen, this diluent B being, in addition or alternatively, soluble to a proportion of at least 5%, preferably at least 10% and even more preferably at least 20% by weight in the matrix A.  
     
     
         4 . Composition according to any one of  claims 1  to  3 , characterized in that the silicone diluent B is obtained by hydrosilylation of a synthon bearing an ethylenically unsaturated function and a function FrA using a silicone oil, in the presence of a heterogeneous catalytic composition comprising a metal chosen from the group consisting of Co, Rh, Ru, Pt and Ni, deposited on an inert support.  
     
     
         5 . Composition according to any one of  claims 1  to  4 , characterized in that the diluent (B) corresponds to at least one of the following general formulae:  
       
         
           
           
               
               
           
         
       
       in which: 
 T=R 3  or Si (R 3 ) u (frB) v ,  
 x+y=3; x=1 to 3; y=0 to 3;  
 b+c=2; b, c=0, 1 or 2;  
 u+v=3; u, v=0 to 3;  
 0≦n≦15;  
 R 2  and R 3  are identical or different and correspond to the same definition as that given for R 0  in formula (I), C 1 -C 6  lower alkyl and/or alkoxy radicals being particularly preferred as radicals R 2  and R 3 , respectively,  
 frB being as defined above in the passage which concerns the substituent Z of formula (I),  
                     
 in which:  
 d+e=2; d=1 or 2; e=0, 1 or 2;  
 o+p≦15, preferably ≦10; o≧1;  
 R 4  and R 5  are, respectively and together, identical to or different from each other and correspond to the same definition as that of R 2  given above.  
 
     
     
         6 . Composition according to any one of  claims 1  to  5 , characterized in that the functions frB are chosen from the following radicals:  
       
         
           
           
               
               
           
         
         with R 6 : 
 optionally substituted linear or branched C 1 -C 12  alkylene,  
 or arylene, preferably phenylene, optionally substituted, preferably with one to three C 1 -C 6  alkyl groups,  
 
         with R 7 =linear or branched C 1 -C 6  alkyl.  
       
     
     
         7 . Composition according to any one of  claims 1  to  6 , characterized in that the diluent (B) consists of at least one functionalized polysiloxane frB of the following formula:  
       
         
           
           
               
               
           
         
       
     
     
         8 . Composition according to any one of  claims 1  to  7 , characterized in that the constituents of the matrix A belong to at least one of the following species: 
 α 1.1 ) cycloaliphatic epoxides, taken alone or as a mixture with each other: 
 epoxides of the type 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexane carboxylate:  
                     
 or bis(3,4-epoxycyclohexyl) adipate, being particularly preferred;  
 
 α 1.2 ) non-cycloaliphatic epoxides, taken alone or as a mixture with each other: 
 epoxides of the type resulting from the coupling of bisphenol A and epichlorohydrin and of the type: 
 alkoxylated bisphenol A di- and triglycidyl ethers of 1,6-hexanediol, of glycerol, of neopentyl glycol and of trimethylolpropane,  
 or bisphenol A diglycidyl ethers,  
 
 alpha-olefin epoxides, NOVOLAC epoxides, epoxidized soybean and linseed oil, and epoxidized polybutadiene,  
 being particularly preferred,  
 
 α 2)  acrylates, taken alone or as a mixture with each other; e.g.: 
 epoxidized acrylates, preferably the oligomer of bisphenol-A-epoxydiacrylate (EBECRYL 600),  
 acrylo-glycero-polyester, preferably mixture of trifunctional acrylate oligomer obtained from glycerol and polyester (EBECRYL 810),  
 multifunctional acrylates, preferably pentaerythrityl triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDODA), trimethylolpropane ethoxylate triacrylate, thiodiethylene glycol diacrylate, tetraethylene glycol diacrylate (1GDA), tripropylene glycol diacrylate (TRPGDA), triethylene glycol diacrylate (TREGDA), trimethylpropane trimethacrylate (TMPTMA),  
 acrylo-urethanes,  
 acrylo-polyethers,  
 acrylo-polyesters,  
 unsaturated polyesters,  
 acrylo-acrylics,  
 being particularly preferred,  
 
 α 3)  linear or cyclic alkenyl ethers, taken alone or as a mixture with each other: 
 vinyl ethers, in particular triethylene glycol divinyl ether (RAPIDCURE® CHVE-3, GAF Chemicals Corp.), cyclic vinyl ethers or acrolein tetramers and/or dimers and the vinyl ether of the following formula:  
                     
 propenyl ethers,  
 and butenyl ethers,  
 being most especially preferred,  
 
 α 4)  polyols taken alone or as a mixture with each other, preferably the compound of the formula given below:  
                     
 
     
     
         9 . Composition according to any one of  claims 1  to  8 , characterized in that the proportions of compounds A/B/C are as follows:  
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                     
                 
                     
                   A: 
                   59-97.99%, 
                   preferably 70-97.9%, 
                 
                     
                   B: 
                   39-1%, 
                   preferably 29-1%; 
                 
                     
                   C: 
                    2-0.01%, 
                   preferably  1-0.1%. 
                 
                     
                     
                 
                     
                     
                 
             
                
                
               
               
                
                
                
                
                
               
            
           
         
       
     
     
         10 . Composition according to any one of  claims 1  to  10 , characterized: 
 in that it comprises: 
 a matrix (A) based on a mixture of at least one of the following species: epoxides (α 1 ), acrylates (α 2 ), vinyl ethers (α 3 ), polyols (α 4 ), preferably (α 1 ) and (α 2 ),  
 and a silicone diluent (B) in which the functions frB are epoxy and/or acrylate and/or vinyl ether and/or hydroxyl, preferably epoxy and/or acrylate,  
 and in that when the species used are (α 1 ) and/or (α 3 ), then the photoinitiator (C) is a cationic polyamino acid, whereas, for the species (α 2 ) and (α 4 ), the polyamino acid is a radical polyamino acid.  
 
 
     
     
         11 . Use of the silicone diluent (B), as defined in one of claims  1  and  3  to  7 , for the preparation of a composition, preferably an ink or a varnish, which can undergo cationic and/or radical polymerization and/or crosslinking by irradiation, preferably actinic irradiation, and/or by a beam of electrons, the said composition also comprising compounds A and C and, optionally, D, E and F targetted in  claim 1.